Metalliferous azoic dyes



Patented Dec. 20, 1949 TUNITED STATES PATENT OFFICE METALLIFEROUS AZOIC DYES Julius Miller and Eugene A. Markush, Newark, N. J assignors to Pharma Chemical Corporation, New York, N. Y., a corporation of New York . ,No Drawing. Application February 24, 1945, Serial No. 579,688

'12 Claims. (Cl. 8-42) OH 3) NH-C o-Nii to react with, or more explicitly to couple with,

two moles of a diazo'n'ium compound or one mole of a tetrazo compound in the presence of suitable metalizing agents'such as water-soluble salts of chromium, copper, nickel, etc.

The 'diazonium and tetraz'onium are applied preferably in the form of stabilized diazoniums, namely, diazoamino or diazo-imino compounds. The final product may also be obtained by, applying the amine as nitrosamine.

It will be noted that the stabilizing compound does not enter into the finished dye, its sole use being to stabilize the diazo compound until it is required for combination with the coupling component.

The bis-azo-nitroso compound is a dinitroso derivative of 4-4-dihydroxy-3-3' -diamino-diphenyl-urea described in our co-pending patent application, Serial Number 562,388, filed"NoVem- The resulting brown dyes have the probable general formula, but we are not sure orcertain, however, of the indicatedlinkages of the metal atom.

R=any diazotisable aromatic amine residue.

X=any substituent such as halogen, nitro, alkyl, aryl, alkoxy, aryloxy, but not any rendering solubility in water such as sulfonic, carboxylic or tertiary amines. me=metal such as chromium, copper and nickel which are capable of forming metal azo complex compounds.

The bis-azo-nitroso compound is made accorde ing to the following synthesis:

Para-nitro-ortho-amino-phenol is acetylated to para-nitro-ortho-acetyl-amido-pheno1. compound is reduced to para-amido-ortho-acetylamido-phenyl and subsequently treated with carbonyl-chloride. Theacetyl groups are hydrolyzed 011?, and the resultant diamido compound, upon treatment with sodium nitrite in the presence of hydrochloric acid, yields 3-3-tetrazoniumchloride-4-4-dihydroxy 5-5 dinitroso diphenyle urea. When coupled with resorcinol, the 5-5dinitroso-4-4' dihydroxy-diphenyl 3-3'-bis-azo-,Q

resorcinol is obtained.

A more specific adaptation of the step in this process for the synthesis of the dinitrosodiazo compound isas follows: 30%; parts of 4-4'-dihydroxy-3-3-diamino-diphenyl-urea are slurried in 1000 parts of cold water, and parts of hydrochloric acid, and cooled with ice to 0-5 C. and treated with 35 parts of sodium nitrite in solution. The solution is stirred for A,; hour and filtered. The compound thus formed has After the coupling with the resorcinol, there is obtained the compound having the structure:

, OH NO N=NOOH I NE This dye, when dry, is a black lustrous crystalline powder readily soluble in caustic alkaline solutions. This dye combines with two molecules of diazonium to form polyazo dyes which are easily converted into metalized dyes. These metalliferous colors have excellent fastness, and the whole procedure for their formation is readily achieved by the well-known printing methods used in the art. These methods we now describe and will further disclose the scope of our invention.

Example I 25.3 parts of the diazo-imino resulting from the condensation of diazotised o-amino-cliphenyl ether and proline are mixed with 12.6 parts of -5'-dinitroso -4-4'- dihydroxy diphenyl-urea- 3-3'-bis azo resorcinol, the latter hereinafter called urea-dye for the sake of simplicity.

'This is covered with 25 parts of Cellosolve (ethylene glycol monoethyl-ether), 332.0 parts of water and 25.6 parts sodium hydroxide solution 32 B. Upon stirring, a clear brown solution results. This is then thickened with 579.5 parts starch-tragacanth paste commonly used in textile printing. The mass is stirred until a homogenous paste is obtained, then 40 parts of a 26.4% neutral sodium chromate solution are added and again stirred until uniform consistency is attained.

Cotton cloth is printed with this paste, and aged for 3 to 5 minutes in a live steam ager in the presence of acetic or formic acid or a mixture of both. Upon subsequent rinsing, hot soaping, rinsing and drying, there results a deep rich seal brown shade, the probable formula or which is:

Example II 1000 parts of a printing paste are prepared as follows:

35.34 parts of the bls-diazoimino resulting from the condensation of diazotised 4-chlor-2-aminoanisol and ethylene-diamino diacetic acid.

12.6 parts urea dye 25 parts glycol-monoethyl-ether 25.6 parts sodium hydroxide solution 32 B. 320parts water This mixture is stirred to solution and thickened with sufficient starch-tragacanth paste to total 960 parts. 40 parts of neutral sodium chromate solution 26.4% by weight are incorporated into the paste.

Cotton cloth printed with this color paste yields, after the treatment described in Example I, a deep brown shade somewhat yellower than that described in the previous example.

The probable formula is:

Cr /Cr 0 Example III Cloth is printed with a printing paste pre-:

pared as follows:

28 parts of the diazoamino resulting from the condensation of diazotised para-phenetidine and alphacarboxy-piperidine.

12.6 parts urea dye 25 parts Cellosolve (ethylene-glycol-monoethylether) 25.6 parts sodium hydroxide solution 32 B.

327 parts of water 542 parts starch-tragacanth paste To this is added 40 parts of a mixture prepared of:

25 parts CuSO4, 5H2O 15 parts tartaric acid 10 parts NaOH 50 parts water After printing and subsequent treatment as above, there results a reddish brown.

Examples 1V "I2 6 elt s ur ef xe" 1 a t 'mt w l s v 2- ft i hi h d irle qlut qmg": B- 359partswatec Thlckened' with 'a" quantity oistarch tragacamnpa st serum-9605mm 4o"parts "of: 'sodiiii'n chi'omatesomtion- 26 .4 The resultant shade after the described treatment is a dark brown with a purple cast. The probable formula is:

zxamp ei imparts of :the diazoimino resulting from diazo tis ed-cresidiheand prolihe are frii x'ed witlig s hxdroxide. splutioru Whenall sl i sqlved, starch traea a p t is added smthat the, totalrweighs. BBQ-parts":

flanfirilsgof asolutltmofi sodium: nickeltartrate brepapedg.fnomq-nickehsulfatei tartariciacid. and; 'sbdi m't mmxideh This paste is then printed on cotton cloth a dz; ated asides n b -hererr ult a deeplbn vna-l print.

The probable formula is:

Example Y]; 1

Suflicient sodium nitrosamiue of 5-nitro-2 toluidinel'containing theeequiva'lent of.-6.1 lbs: of 100%: 5-.nitro.-2;.-toluidineislpasted with 12.6 lbs.

of urea dye, 4-.illslbs.w of sodiumhydroxide 40 B., fiil'tlbs. oflethylene' glycolmor oethyl ether suflicient water to make a total'of: 500 lbs. Upon stirring;- asolution results whic h'is' thickened with alkaline starch tragacanth pasteand: 40 1bs. of sodium copper tartrate preparedas previously described. The total weight of the printing paste is 1000 lbs The paste is printed on cotton cloth and after aging in the presence-of live steam and aceticformic acid vapors for five minutes, subsequent hot soaping, rinsingjand drying, there results a chocolate brown priiit.

The probable formula is:

N=N, 0 OH:

The stabilizersw do not constitute. any, claim i of: Bi-Minventiom.andtxwei do; not limit; ourselves to. We found-that,

thosementionedjimtheexamples, abil zers; listed; herewith or; selected from the groumindieatedz by. any: individual stabilizer... re.- rded-herewith. cvan;be. .suc.eessiu1ly appl d:

4-s.u1f o -2-,amino1benzoic. acid? 4-sulfor2emethylamino-benzoic acid... Butylaminoa-cetic acid Trimethylene+bis;-eliminwacetic aeidla Penta-methylene-bis-(imino-propionic acid) MethvlenesbisAmino-acetic acidm Dicyandiamide Ethanol-amino-ethane-sulfonamide-acetic acid P-phenylene-diamine-disulfonic acid Guanyl-taurine Diethanol-amine 3-tetra-methylensulfone-glycine Methyl glucamine Piperidine-alpha-carboxylic acid The following table further illustrates the dyes resulting from the combination of diazoni'ums of amines coupled with the urea compound in the presence of the salts of the designated metals.

8 5. As a composition of. matter a mixture, adapted for printing cellulosic textile materials comprising a quantity of -5'-di-nitroso-4-4' dihydroxy-diphenyl-urea-3-3-bis azo resorclnol and the molecular quantity of a stabilized diazotized aromatic amine, devoid of sulfonic, carboxylic and tertiary amine groups, sufllcient for his coupling and having at least one substituent selected from the group consisting of halogen,

0 nitro, alkyl, aryl, alkoxy and aryloxy, and a water-soluble salt of a member of the group consisting of chromium, copper and nickel, in amount Diazo Compounds of Amines Shade l-methyl-2-amlno-benzene. l-amino-2-4dimethyl-benzene l-amiuo-fi-chlor-beuzeue Aniline 2-amiuo-naphthalene l-amino-tmethoxy-benze l-amino-l-methyl-benzene 1-amin0-napthalene a l-amino-Z:4-diethoxy-benzenel-amino-2-methoxy-benzene 44'-diamino-3-3-dichlor-dipheuyl. 1-amino-3-methyl-be11zene ,l l-methyl-3-benzoyl-amin0-4-chlor-S-ammo-benzene 4-4-diamino-diphenyl-methane 1-methyl-2-amiuo-5-nitro-benzene l Deep Brown.

Do. Bright Chocolate Brown. Brown Purple Cast. Brown. Very deep Brown Purple Cast. Full deep Brown. Brown. Seal Brown. Deep Reddish Brown. Seal Brown. Deep Brown Purple Cast. Seal Brown.

Do. Chocolate Brown. Seal Brown Reddish Cast.

in which R is a diazotizable aromatic amine residue, devoid of sulfonic, carboxylic, and tertiary amine groups; X is a substituent selected from the group consisting of halogen, nitro, alkyl, aryl, alkoxy, and aryloxy, and Y is selected from the group consisting of hydrogen and the members of group X; Me is a member of the group consisting of chromium, copper, and nickel; the said compounds being formed and deposited upon the fibers of cellulosic textile material, and when so produced, yielding deep brown shades of marked fastness to light, washing, and chlorine.

2. A compound of claim 1 in which me is ch'romium.

3. A compound of claim 1 in which me is copper. ,1 I

4. A compound of claim 1 in which nickel.

..me is suificient to provide 4 atoms of the metal per molecule.

6. As a composition of matter a mixture, adapted for printing cellulosic textile materials, comprising a quantity of 5-5'-di-nitroso-44 dihydroxydiphenylurea-3-3'-bis azo resorcinol and the molecular quantity of a stabilized diazotized aromatic amine, devoid of sulfonic, carboxylic and tertiary amine groups, sufficient for his coupling and having at least one substituent selected from the group consisting of halogen, nitro, alkyl, aryl, alkoxy and aryloxy, and a water-soluble salt of chromium, in amount sufiicient to provide 4 atoms of the metal per molecule. .o

7. As a composition of matter a mixture adapted for printing cellulosic textile materials, comprising a quantity of 5-5'-di-nitroso-4-4' dihydroxy-diphenyl-urea-3-3'-bis azo resorcinol and the molecular quantity of a stabilized diazotized aromatic amine, devoid of sulfonic, carboxylic and tertiary amine groups, sufilcient for bis coupling and having at least one substituent selected from the group consisting of halogen, nitro, alkyl, aryl, alkoxy, and aryloxy, and a water-soluble salt of copper, in amount sufficient to provide 4 atoms of the metal per molecule.

8. As a composition of matter a mixture, adapted for printing cellulosic textile materials, comprising a quantity of 5-5-di-nitroso-4-4' dihydroxy-diphenyl-urea-3-3'-bis azo resorcinol and the molecular quantity of a stabilized diazotized aromatic amine, devoid of sulfonic, carboxylic and tertiary amine groups, sufiicient for bis coupling and having at least one substituent selected from the group consisting of halogen,

nitro, alkyl, aryl, alkoxy and aryloxy, and a water-soluble salt of nickel, in amount sufficient to provide 4 atoms of the metal per molecule.

9. Cellulosie textile material having developed thereon and adsorbed thereto an insoluble dye stuff by a composition of matter of claim 5.

10. Cellulosic textile material having developed thereon and adsorbed thereto an insoluble dyestuiT by a composition of matter of claim 6.

9 11. Cellulosic textile material having developed thereon and adsorbed thereto an insoluble dyestufi by a composition of matter of claim 7.

12. Cellulosic textile material having developed thereon and adsorbed thereto an insoluble dyestufi by a composition of matter of claim 8.

JULIUS MILLER. EUGENE A. MARKUSH.

REFERENCES CITED UNITED STATES PATENTS Name Date Kahn Jan. 11, 1910 Number Number 10 Number Name Date Anderwert et a1. Oct. 22, 1918 Anderwert et a1. Jan. 21, 1919 Haller et al. Oct. 11, 1932 Brightman et a1 Nov. 7, 1933 Sparks et al Jan. 14, 1941 Straub Sept. 30, 1947 FOREIGN PATENTS Country Date Great Britain 1910 Great Britain Jan. 4, 1917 France Jan. 22, 1936 

